The present invention relates to packaging films made of polyethylene.
A great number of films have been hitherto produced, and films having properties appropriate for the purpose have been selected and employed. Above all, films produced from linear low-density polyethylene are extensively employed, but they differ from one another in the properties depending upon the type of the monomer units constituting the polyethylene or the type of the process for preparing the polyethylene.
For example, films produced from a linear low-density ethylene/1-butene copolymer have excellent transparency and surface smoothness, but they easily suffer tearing in the molding process because their mechanical strength properties indicated by dart impact strength and Elmendorf tear strength are low, and hence there is a limit of increasing a molding speed.
On the other hand, films produced from linear low-density polyethylene prepared by the use of a metallocene catalyst which has been recently highlighted are known as films hardly suffering blocking because the linear low-density polyethylene has a narrow composition distribution. Especially when a linear low-density ethylene/1-hexene copolymer prepared by the use of a metallocene catalyst is used to produce films, the resulting films exhibit excellent mechanical strength, transparency and heat sealing properties. However, if the melt flow rate (MFR) of the linear low-density ethylene/1-hexene copolymer is low, e.g., not more than 1 g/10 min, melt fracture easily takes place, and as a result, the films have poor surface smoothness.
Accordingly, there is desired development of high-strength packaging films capable of being produced at a high speed with retaining properties inherent in films of linear low-density polyethylene, such as transparency and surface smoothness.
It is an object of the present invention to provide packaging films which exhibit excellent mechanical strength properties such as high dart impact strength with retaining properties inherent in films of linear low-density polyethylene, such as transparency and surface smoothness.
It is another object of the invention to provide films having such excellent low-temperature properties (e.g., low-temperature drop-bag strength properties) that they can be satisfactorily used for heavy-duty packaging bags even in the cold districts having below-zero temperatures.
The first ethylene resin packaging film according to the invention is an ethylene resin packaging film comprising an ethylene/xcex1-olefin copolymer (A) which is a copolymer obtained by copolymerizing ethylene and an xcex1-olefin of 6 to 20 carbon atoms in the presence of an olefin polymerization catalyst comprising (a) a compound of a transition metal of Group IV of the periodic table, said compound (a) containing a ligand having cyclopentadienyl skeleton, and (b) an organoaluminum oxy-compound, and which has the following properties:
(i) the density is in the range of 0.918 to 0.935 g/cm3,
(ii) the melt flow rate (MFR (g/10 min)) at 190xc2x0 C. under a load of 2.16 kg is in the range of 0.05 to 2.0 g/10 min,
(iii) the decane-soluble component fraction (W (% by weight) at room temperature and the density (d (g/cm3)) satisfy the following relation
xe2x80x83W less than 80xc3x97exp(xe2x88x92100(dxe2x88x920.88))+0.1,
(iv) the flow index (FI (l/sec)), which is defined as a shear rate at which the shear stress of said copolymer in a molten state at 190xc2x0 C. reaches 2.4xc3x97106 dyne/cm2, and the melt flow rate (MFR (g/10 min)) satisfy the following relation
xe2x80x83FI greater than 75xc3x97MFR, and
(v) the melt tension (MT (g)) at 190xc2x0 C. and the melt flow rate (MFR (g/10 min)) satisfy the following relation
xe2x80x83MT greater than 2.2xc3x97MFRxe2x88x920.84,
preferably 5.5xc3x97MFR0.65 greater than MT greater than 2.2xc3x97MFRxe2x88x920.84.
It is preferable that the ethylene/xcex1-olefin copolymer (A) further has the following property:
the mean value (B1) of the numbers of branches on the higher molecular weight side, as determined by GPC-IR, and the mean value (B2) of the numbers of branches on the lower molecular weight side, as determined by GPC-IR, satisfy the following relation
xe2x80x83B1xe2x89xa7B2.
The second ethylene resin packaging film according to the invention is an ethylene resin packaging film comprising an ethylene/xcex1-olefin copolymer composition (B) which comprises:
(I) 50 to 99 parts by weight of an ethylene/xcex1-olefin copolymer (a-1), and
(II) 1 to 50 parts by weight of high-density polyethylene (b-1),
wherein the ethylene/xcex1-olefin copolymer (a-1) is a copolymer obtained by copolymerizing ethylene and an xcex1-olefin of 6 to 20 carbon atoms in the presence of an olefin polymerization catalyst comprising (a) a compound of a transition metal of Group IV of the periodic table, said compound (a) containing a ligand having cyclopentadienyl skeleton, and (b) an organoaluminum oxy-compound, and has the following properties:
(i) the density is in the range of 0.900 to 0.935 g/cm3,
(ii) the melt flow rate (MFR (g/10 min)) at 190xc2x0 C. under a load of 2.16 kg is in the range of 0.01 to 1.0 g/10 min,
(iii) the decane-soluble component fraction (W (% by weight)) at room temperature and the density (d (g/cm3)) satisfy the following relation
xe2x80x83W less than 80xc3x97exp(xe2x88x92100(dxe2x88x920.88))+0.1,
(iv) the flow index (FI (l/sec)), which is defined as a shear rate at which the shear stress of said copolymer in a molten state at 190xc2x0 C. reaches 2.4xc3x97106 dyne/cm2, and the melt flow rate (MFR (g/10 min)) satisfy the following relation
xe2x80x83FI greater than 75xc3x97MFR,
(v) the melt tension (MT (g)) at 190xc2x0 C. and the melt flow rate (MFR (g/10 min)) satisfy the following relation
xe2x80x83MT greater than 2.2xc3x97MFRxe2x88x920.84,
preferably 5.5xc3x97MFRxe2x88x920.65 greater than MT greater than 2.2xc3x97MFRxe2x88x920.84, and
(vi) the temperature (Tm (xc2x0 C.)) at the maximum peak position in an endothermic curve of said copolymer (a-1), as measured by a differential scanning calorimeter (DSC), and the density (d) satisfy the following relation
xe2x80x83Tm less than 400dxe2x88x92250; and
the high-density polyethylene (b-1) is ethylene monopolymer or ethylene/xcex1-olefin copolymer obtained by copolymerizing ethylene and an xcex1-olefin of 3 to 20 carbon atoms, which has the following properties:
(i) the density is in the range of 0.935 to 0.975 g/cm3, and
(ii) the melt flow rate (MFR (g/10 min)) at 190xc2x0 C. under a load of 2.16 kg is in the range of 0.1 to 100 g/10 min.
The ethylene resin packaging films mentioned above preferably have (A) a Young""s modulus of not less than 4,000 kg/cm2 and (B) a dart impact strength of not less than 55 kg/cm.
The third ethylene resin packaging film according to the invention is an ethylene resin packaging film comprising an ethylene/xcex1-olefin copolymer composition (C) which comprises:
(I) 1 to 50 parts by weight of an ethylene/xcex1-olefin copolymer (a-2), and
(II) 50 to 99 parts by weight of an ethylene copolymer (b-2),
wherein the ethylene/xcex1-olefin copolymer (a-2) is a copolymer obtained by copolymerizing ethylene and an xcex1-olefin of 4 to 12 carbon atoms in the presence of an olefin polymerization catalyst comprising (a) a compound of a transition metal of Group IV of the periodic table, said compound (a) containing a ligand having cyclopentadienyl skeleton, and (b) an organoaluminum oxy-compound, and has the following properties:
(i) the density is in the range of 0.880 to 0.925 g/cm3,
(ii) the melt flow rate (MFR (g/10 min)) at 190xc2x0 C. under a load of 2.16 kg is in the range of 0.01 to 5.0 g/10 min,
(iii) the decane-soluble component fraction (W (% by weight)) at room temperature and the density (d (g/cm3)) satisfy the following relation
xe2x80x83W less than 80xc3x97exp(xe2x88x92100(dxe2x88x920.88))+0.1,
(iv) the flow index (FI (l/sec)), which is defined as a shear rate at which the shear stress of said copolymer in a molten state at 190xc2x0 C. reaches 2.4xc3x97106 dyne/cm2, and the melt flow rate (MFR (g/10 min)) satisfy the following relation
xe2x80x83FI greater than 75xc3x97MFR, and
(v) the melt tension (MT (g)) at 190xc2x0 C. and the melt flow rate (MFR (g/10 min)) satisfy the following relation
xe2x80x83MT greater than 2.2xc3x97MFRxe2x88x920.84,
xe2x80x83preferably 5.5xc3x97MFRxe2x88x920.65 greater than MT greater than 2.2xc3x97MFRxe2x88x920.84; and
the ethylene copolymer (b-2) is a copolymer obtained by copolymerizing ethylene and an xcex1-olefin of 4 to 10 carbon atoms and has the following properties:
(i) the density is in the range of 0.920 to 0.945 g/cm3,
(ii) the melt flow rate (MFR (g/10 min)) at 190xc2x0 C. under a load of 2.16 kg is in the range of 0.1 to 10 g/10 min, and
(iii) the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), Mw/Mn, is in the range of 3 to 6.
This ethylene resin packaging film preferably has (B) a dart impact strength of not less than 250 kg/cm and (C) an Elmendorf tear strength of not less than 60 kg/cm in the machine direction.
The first ethylene resin packaging film according to the invention is made of an ethylene/xcex1-olefin copolymer (A). The ethylene/xcex1-olefin copolymer (A) is described below.
The ethylene/xcex1-olefin copolymer (A) for use in the invention comprises ethylene and an xcex1-olefin of 6 to 20 carbon atoms.
Examples of the xcex1-olefins of 6 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and 1-dodecene.
In the ethylene/xcex1-olefin copolymer (A) for use in the invention, the ethylene content is in the range of usually 94 to 99% by mol, preferably 96 to 98% by mol, and the content of the xcex1-olefin that is a comonomer is in the range of usually 1 to 6% by mol, preferably 2 to 4% by mol.
The ethylene/xcex1-olefin copolymer (A) for use in the invention desirably has a density of 0.918 to 0.935 g/cm3, preferably 0.905 to 0.930 g/cm3.
The ethylene/xcex1-olefin copolymer (A) for use in the invention desirably has a melt flow rate (MFR), as measured at 190xc2x0 C. under a load of 2.16 kg, of 0.05 to 2.0 g/10 min, preferably 0.1 to 2.0 g/10 min.
The ethylene/xcex1-olefin copolymer (A) for use in the invention has the following relation between the decane-soluble component fraction (W (% by weight) at room temperature and the density (d (g/cm3)):
W less than 80xc3x97exp(xe2x88x92100(dxe2x88x920.88))+0.1,
preferably W less than 60xc3x97exp(xe2x88x92100(dxe2x88x920.88))+0.1.
The ethylene/xcex1-olefin copolymer (A) for use in the invention has the following relation between the flow index (FI (l/sec)), which is defined as a shear rate at which the shear stress of said copolymer in a molten state at 190xc2x0 C. reaches 2.4xc3x97106 dyne/cm2, and the melt flow rate (MFR (g/10 min)):
FI greater than 75xc3x97MFR,
preferably FI greater than 80xc3x97MFR.
The linear ethylene/xcex1-olefin copolymer (A) for use in the invention has the following relation between the melt tension (MT (g)) at 190xc2x0 C. and the melt flow rate (MFR (g/10 min)):
MT greater than 2.2xc3x97MFRxe2x88x920.84,
preferably 5.5xc3x97MFRxe2x88x920.65 greater than MT greater than 2.2xc3x97MFRxe2x88x920.84,
more preferably 5.5xc3x97MFRxe2x88x920.65 greater than MT greater than 2.5xc3x97MFRxe2x88x920.84.
The ethylene/xcex1-olefin copolymer (A) for use in the invention has the following relation between the mean value (B1) of the numbers of branches on the higher molecular weight side, as determined by GPC-IR, and the mean value (B2) of the numbers of branches on the lower molecular weight side thereof, as determined by GPC-IR:
B1xe2x89xa7B2.
The mean value (B1) of the numbers of branches on the higher molecular weight side, as determined by GPC-IR, is a mean value of the numbers of branches on the higher molecular weight side out of two divisions of the branch numbers measured within the range of 15 to 85% of the cumulative weight fraction of high-molecular weight eluates fractionated on the molecular weight by GPC (i.e., high-molecular weight eluate component except 15% of the low-molecular weight region and 15% of the high-molecular weight region). The mean value (B2) of the numbers of branches on the lower molecular weight side is a mean value on the lower molecular weight side out of said two divisions.
The conditions for the measurements of B1 and B2 are as follows.
Measuring device: PERKIN ELMER 1760X
Column: TOSOH TSKgel GMMH-HT (7.5 mmI.D.xc3x97600 mm)xc3x971
Eluent: o-dichlorobenzene (ODCB) containing 0.05% of MP-J (available from Wako Junyaku Kogyo, extra pure grade)
Column temperature: 140xc2x0 C.
Sample concentration: 0.1% (weight/volume)
Injection volume: 100 microliters
Detector: MCT
Resolution: 8 cmxe2x88x921 
The ethylene/xcex1-olefin copolymer (A) having the above relation between B1 and B2 exhibits a narrow composition distribution and has a low content of the low-molecular weight polymer portion, so that the copolymer (A) hardly suffers stickiness.
The ethylene/xcex1-olefin copolymer (A) can be favorably used for packaging films.
The ethylene/xcex1-olefin copolymer (A) can be prepared by copolymerizing ethylene and an xcex1-olefin of 6 to 20 carbon atoms in the presence of an olefin polymerization catalyst comprising:
(a) a compound of a transition metal of Group IV of the periodic table, which contains a ligand having cyclopentadienyl skeleton,
(b) an organoaluminum oxy-compound,
(c) a carrier, and optionally
(d) an organoaluminum compound, in such a manner that the resulting polymer has a density of 0.918 to 0.935 g/cm3.
The olefin polymerization catalyst and the catalyst components are described below.
(a) Transition Metal Compound
The compound (a) of a transition metal of Group IV of the periodic table, which contains a ligand having cyclopentadienyl skeleton, (sometimes referred to as a xe2x80x9ccomponent (a)xe2x80x9d hereinafter) is a transition metal compound represented by the following formula (I):
ML1xxe2x80x83xe2x80x83(I)
wherein M is a transition metal atom selected from Group IV of the periodic table; L1 is a ligand coordinated to the transition metal atom, at least two ligands L1 are each a substituted cyclopentadienyl group having 2 to 5 substituents selected from methyl and ethyl, and the ligand L1 other than the substituted cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom; and x is a valence of the transition metal atom M.
L1 is a ligand coordinated to the transition metal atom M, and at least two ligands L1 are each a substituted cyclopentadienyl group having 2 to 5 substituents selected from methyl group and ethyl group. The ligands may be the same or different. The substituted cyclopentadienyl group is a substituted cyclopentadienyl group having two or more substituents, preferably a substituted cyclopentadienyl group having 2 or 3 substituents, more preferably a di-substituted cyclopentadienyl group, particularly preferably a 1,3-substituted cyclopentadienyl group. The substituents may be the same or different.
In the formula (I), M is a transition metal atom selected from Group IV of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium.
In the formula (I), the ligand L1 other than the substituted cyclopentadienyl group coordinated to the transition metal atom M is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom.
Examples of the transition metal compounds represented by the formula (I) include:
bis(cyclopentadienyl)zirconium dichloride,
bis(methylcyclopentadienyl)zirconium dichloride,
bis(ethylcyclopentadienyl)zirconium dichloride,
bis(n-propylcyclopentadienyl)zirconium dichloride,
bis(n-butylcyclopenadienyl)zirconium dichloride,
bis(n-hexylcyclopentadienyl)zirconium dichloride,
bis(methyl-n-propylcyclopentadienyl)zirconium dichloride,
bis(methyl-n-butylcyclopentadienyl)zirconium dichloride,
bis(dimethyl-n-butylcyclopentadienyl)zirconium dichloride,
bis(n-butylcyclopentadienyl)zirconium dibromide,
bis(n-butylcyclopentadienyl)zirconium methoxychloride,
bis(n-butylcyclopentadienyl)zirconium ethoxychloride,
bis(n-butylcyclopentadienyl)zirconium butoxychloride,
bis(n-butylcyclopentadienyl)zirconium ethoxide,
bis(n-butylcyclopentadienyl)zirconium methylchloride,
bis(n-butylcyclopentadienyl)zirconium dimethyl,
bis(n-butylcyclopentadienyl)zirconium benzylchloride,
bis(n-butylcyclopentadienyl)zirconium dibenzyl,
bis(n-butylcyclopentadienyl)zirconium phenylchloride,
bis(n-butylcyclopentadienyl)zirconium hydride chloride,
bis(dimethylcyclopentadienyl)zirconium dichloride,
bis(di-ethylcyclopentadienyl)zirconium dichloride,
bis(methylethylcyclopentadienyl)zirconium dichloride,
bis(dimethylethylcyclopentadienyl)zirconium dichloride,
bis(dimethylcyclopentadienyl)zirconium dibromide,
bis(dimethylcyclopentadienyl)zirconium methoxychloride,
bis(dimethylcyclopentadienyl)zirconium ethoxychloride,
bis(dimethylcyclopentadienyl)zirconium butoxychloride,
bis(dimethylcyclopentadienyl)zirconium diethoxide,
bis(dimethylcyclopentadienyl)zirconium methylchloride,
bis(dimethylcyclopentadienyl)zirconium dimethyl,
bis(dimethylcyclopentadienyl)zirconium benzylchloride,
bis(dimethylcyclopentadienyl)zirconium dibenzyl,
bis(dimethylcyclopentadienyl)zirconium phenylchloride, and
bis(dimethylcyclopentadienyl)zirconium hydride chloride.
In the above examples, the di-substituted cyclopentadienyl rings include 1,2- and 1,3-substituted cyclopentadienyl rings, and the tri-substituted cyclopentadienyl rings include 1,2,3- and 1,2,4-substituted cyclopentadienyl rings. In the present invention, transition metal compounds wherein a zirconium metal is replaced with a titanium metal or a hafnium metal in the above-mentioned zirconium compounds are also employable.
Of the above transition metal compounds represented by the formula (I), particularly preferable are:
bis(n-propylcyclopentadienyl)zirconium dichloride,
bis(n-butylcyclopentadienyl)zirconium dichloride,
bis(1-methyl-3-n-propylcyclopentadienyl)zirconium dichloride,
bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride,
bis(1,3-dimethylcyclopentadienyl)zirconium dichloride,
bis(1,3-diethylcyclopentadienyl)zirconium dichloride, and
bis(1-methyl-3-ethylcyclopentadienyl)zirconium dichloride.
The transition metal compound for use in the invention may be a mixture of two or more kinds of the transition metal compounds represented by the formula (I).
Specifically, there can be mentioned a combination of bis(1,3-n-butylmethylcyclopentadienyl)zirconium dichloride and bis(1,3-dimethylcyclopentadienyl)zirconium dichloride, a combination of bis(1,3-n-propylmethylcyclopentadienyl)zirconium dichloride and bis(1,3-dimethylcyclopentadienyl)zirconium dichloride, and a combination of bis(n-butylcyclopentadienyl)zirconium dichloride and bis(1,3-dimethylcyclopentadienyl)zirconium dichloride.
The transition metal compound for use in the invention may be a mixture of the transition metal compound represented by the formula (I) and a transition metal compound represented by the following formula (II):
MKL2xxe2x88x922xe2x80x83xe2x80x83(II)
wherein M is a transition metal atom selected from Group IV of the periodic table; K and L2 are each a ligand coordinated to the transition metal atom, the ligand K is a bidentate ligand wherein the same or different groups selected from an indenyl group, a substituted indenyl group and their partially hydrogenated products are linked through a lower alkylene group, and the ligand L2 is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom; and x is a valence of the transition metal atom M.
Examples of the transition metal compounds represented by the formula (II) include:
ethylenebis(indenyl)zirconium dichloride,
ethylenebis(4-methyl-1-indenyl)zirconium dichloride, and
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride.
In the present invention, it is preferable to use, as the transition metal compound (a), a combination of at least one compound selected from the transition metal compounds represented by the formula (I) and at least one compound selected from the transition metal compounds represented by the formula (II).
It is desirable that at least one compound selected from the transition metal compounds (a-1) represented by the formula (I) and at least one compound selected from the transition metal compounds (a-2) represented by the formula (II) are used in such amounts that the molar ratio of (a-1)/(a-2) becomes 99/1 to 50/50, preferably 97/3 to 70/30, more preferably 95/5 to 75/25, most preferably 90/10 to 80/20.
(b) Organoaluminum Oxy-compound
The organoaluminum oxy-compound (b) is described below.
The organoaluminum oxy-compound (b) (sometimes referred to as a xe2x80x9ccomponent (b)xe2x80x9d hereinafter) for use in the invention may be benzene-soluble aluminoxane hitherto known or such a benzene-insoluble organoaluminum oxy-compound as disclosed in Japanese Patent Laid-Open Publication No. 276807/1990.
The aluminoxane can be prepared by, for example, the following processes.
(1) An organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing adsorption water or a salt containing water of crystallization, e.g., magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate or cerous chloride hydrate, to react with them, and the aluminoxane is recovered as a hydrocarbon solution.
(2) Water, ice or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran, and the aluminoxane is recovered as a hydrocarbon solution.
(3) An organotin oxide such as dimethyltin oxide or dibutyltin oxide is allowed to react with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene or toluene.
The aluminoxane may contain a small amount of an organometallic component. It is possible that the solvent or the unreacted organoaluminum compound is distilled off from the recovered solution of aluminoxane and the remainder is redissolved in a solvent.
Examples of the organoaluminum compounds used for preparing the aluminoxane include:
trialkylaluminums, such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-secbutylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum;
tricycloalkylaluminums, such as tricyclohexylaluminum and tricyclooctylaluminum;
dialkylaluminum halides, such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride;
dialkylaluminum hydrides, such as diethylaluminum hydride and diisobutylaluminum hydride;
dialkylaluminum alkoxides, such as dimethylaluminum methoxide and diethylaluminum ethoxide; and
dialkylaluminum aryloxides, such as diethylaluminum phenoxide.
Of these, trialkylaluminums and trialkylaluminums are particularly preferable.
Also employable as the organoaluminum compound is isoprenylaluminum represented by the following formula:
(i-C4H9)xAly(C5H10)z
wherein x, y, z are each a positive number, and zxe2x89xa72x.
The organoaluminum compounds mentioned above are used singly or in combination.
Examples of the solvents used for preparing the aluminoxane include aromatic hydrocarbons, such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons, such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions, such as gasoline, kerosine and gas oil; and halogenated products of these aromatic, aliphatic and alicyclic hydrocarbons, particularly chlorinated or brominated products thereof. Also employable are ethers such as ethyl ether and tetrahydrofuran. Of the solvents, aromatic hydrocarbons are particularly preferable.
The benzene-insoluble organoaluminum oxy-compound contains not more than 10% (in terms of Al atom), preferably not more than 5%, particularly preferably not more than 2%, of an Al component that is soluble in benzene at 60xc2x0 C., and is insoluble or sparingly soluble in benzene.
The solubility of the organoaluminum oxy-compound in benzene can be determined in the following manner. The organoaluminum oxy-compound in an amount corresponding to 100 mxc2x7atom of Al is suspended in 100 ml of benzene, and they are mixed at 60xc2x0 C. for 6 hours with stirring. Then, the mixture is subjected to hot filtration at 60xc2x0 C. using a jacketed G-5 glass filter, and the solid separated on the filter is washed four times with 50 ml of benzene at 60xc2x0 C. to obtain filtrates. The amount (x mmol) of Al atom present in all of the filtrates is measured to determine the solubility (x %).
(c) Carrier
The carrier (c) for use in the invention is an inorganic or organic compound of granular or particulate solid having a particle diameter of 10 to 300 xcexcm, preferably 20 to 200 xcexcm. The inorganic carrier is preferably a porous oxide, and examples thereof include SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, and mixtures thereof such as SiO2xe2x80x94MgO, SiO2xe2x80x94Al2O3, SiO2xe2x80x94TiO2, SiO2xe2x80x94V2O5, SiO2xe2x80x94Cr2O3 and SiO2xe2x80x94TiO2xe2x80x94MgO. Of these, preferable are oxides containing at least one component selected from the group consisting of SiO2 and Al2O3 as their major component.
The inorganic oxides may contain small amounts of carbonate, sulfate, nitrate and oxide components, such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O and Li2O.
Although the carriers (c) differ in the properties depending upon the type and the preparation process, the carrier preferably used in the invention desirably has a specific surface area of 50 to 1,000 m2/g, preferably 100 to 700 m2/g, and a pore volume of 0.3 to 2.5 cm3/g. If desired, the carrier is calcined at a temperature of 100 to 1,000xc2x0 C., preferably 150 to 700xc2x0 C., prior to use.
Also employable as the carrier in the invention is an organic compound of granular or particulate solid having a particle diameter of 10 to 300 xcexcm. Examples of such organic compounds include (co)polymers produced using an xcex1-olefin of 2 to 14 carbon atoms such as ethylene, propylene, 1-butene or 4-methyl-1-pentene as a main component, and (co)polymers produced using vinylcyclohexane or styrene as a main component.
(d) Organoaluminum Compound
The olefin polymerization catalyst used for preparing the ethylene/xcex1-olefin copolymer for use in the invention is formed from the component (a), the component (b) and the carrier (c), but an organoaluminum compound (d) may be used, if necessary.
The organoaluminum compound (d) (sometimes referred to as a xe2x80x9ccomponent (d)xe2x80x9d hereinafter) optionally used in the invention is, for example, an organoaluminum compound represented by the following formula (III):
R1nAlX3xe2x88x92nxe2x80x83xe2x80x83(III)
wherein R1 is a hydrocarbon group of 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 3.
In the formula (III), R1 is a hydrocarbon group of 1 to 12 carbon atoms, e.g., an alkyl group, a cycloalkyl group or an aryl group. Examples of such groups include methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl and tolyl.
Examples of such organoaluminum compounds include:
trialkylaluminums, such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum and tri-2-ethylhexylaluminum;
alkenylaluminums, such as isoprenylaluminum;
dialkylaluminum halides, such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide;
alkylaluminum sesquihalides, such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide;
alkylaluminum dihalides, such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide; and
alkylaluminum hydrides, such as diethylaluminum hydride and diisobutylaluminum hydride.
Also employable as the organoaluminum compound (d) is a compound represented by the following formula (IV):
R1nAlY3xe2x88x92nxe2x80x83xe2x80x83(IV)
wherein R1 is the same hydrocarbon as indicated by R1 in the formula (III); Y is xe2x80x94OR2 group, xe2x80x94OSiR33 group, xe2x80x94OAlR42 group, xe2x80x94NR52 group, xe2x80x94SiR63 group or xe2x80x94N(R7)AlR82 group; n is 1 to 2; R2, R3, R4 and R8 are each methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl or the like; R5 is hydrogen, methyl, ethyl, isopropyl, phenyl, trimethylsilyl or the like; and R6 and R7 are each methyl, ethyl or the like.
Examples of such organoaluminum compounds include:
(1) compounds represented by R1nAl(OR2)3xe2x88x92n, such as dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum methoxide;
(2) compounds represented by R1nAl(OSiR33)3xe2x88x92n, such as Et2Al(OSiMe3), (iso-Bu)2Al(OSiMe3) and (iso-Bu)2Al(OSiEt3);
(3) compounds represented by R1nAl(OAlR42)3xe2x88x92n, such as Et2AlOAlEt2 and (iso-Bu)2AlOAl(iso-Bu)2;
(4) compounds represented by R1nAl(NR52)3xe2x88x92n, such as Me2AlNEt2, Et2AlNHMe, Me2AlNHEt, Et2AlN(SiMe3)2 and (iso-Bu)2AlN(SiMe3)2;
(5) compounds represented by R1nAl(SiR63)3xe2x88x92n, such as (iso-Bu)2AlSiMe3; and
(6) compounds represented by R1nAl(N(R7)AlR82)3xe2x88x92n, such as Et2AlN(Me)AlEt2 and (iso-Bu)2AlN(Et)Al(iso-Bu)2.
Of the organoaluminum compounds represented by the formulas (III) and (IV), preferable are compounds represented by the formulas R13Al, R1nAl(OR2)3xe2x88x92n and R1nAl(OAlR42)3xe2x88x92n, and particularly preferable are compounds of said formulas wherein R1 to R4 is an isoalkyl group and n is 2.
In the preparation of the ethylene/xcex1-olefin copolymer (A) for use in the invention, a catalyst prepared by contacting the component (a), the component (b), the carrier (c), and if necessary, the component (d) with one another is employed. Although the components may be contacted in any order, it is preferable to contact the carrier (c) with the component (b), then with the component (a), and then if necessary, with the component (d).
The contact between the components can be carried out in an inert hydrocarbon solvent. Examples of the inert hydrocarbon media used for preparing the catalyst include aliphatic hydrocarbons, such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosine; alicyclic hydrocarbons, such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons, such as benzene, toluene and xylene; halogenated hydrocarbons, such as ethylene chloride, chlorobenzene and dichloromethane; and mixtures of these hydrocarbons.
In the contact between the component (a), the component (b), the carrier (c) and the component (d) optionally used, the component (a) is used in an amount of usually 5xc3x9710xe2x88x926 to 5xc3x9710xe2x88x924 mol, preferably 10xe2x88x925 to 2xc3x9710xe2x88x924 mol, based on 1 g of the carrier (c), and the concentration of the component (a) is in the range of about 10xe2x88x924 to 2xc3x9710xe2x88x922 mol/liter, preferably 2xc3x9710xe2x88x924 to 10xe2x88x922 mol/liter. The atomic ratio (Al/transition metal) of aluminum (Al) in the component (b) to the transition metal in the component (a) is in the range of usually 10 to 500, preferably 20 to 200. The atomic ratio (Al-d/Al-b) of an aluminum atom (Al-d) in the component (d) optionally used to an aluminum atom (Al-b) in the component (b) is in the range of usually 0.02 to 3, preferably 0.05 to 1.5. In the contact between the component (a), the component (b), the carrier (c) and the component (d) optionally used, the mixing temperature is in the range of usually xe2x88x9250 to 150xc2x0 C., preferably xe2x88x9220 to 120xc2x0 C., and the contact time is in the range of usually 1 minute to 50 hours, preferably 10 minutes to 25 hours.
In the olefin polymerization catalyst obtained as above, the transition metal atom derived from the component (a) is desirably supported in an amount of 5xc3x9710xe2x88x926 to 5xc3x9710xe2x88x924 gxc2x7atom, preferably 10xe2x88x925 to 2xc3x9710xe2x88x924 gxc2x7atom, based on 1 g of the carrier (c); and the aluminum atom derived from the component (b) and the component (d) is desirably supported in an amount of 10xe2x88x923 to 5xc3x9710xe2x88x922 gxc2x7atom, preferably 2xc3x9710xe2x88x923 to 2xc3x9710xe2x88x922 gxc2x7atom, based on 1 g of the carrier (c).
The catalyst used for preparing the ethylene/xcex1-olefin copolymer (A) may be a prepolymerized catalyst obtained by prepolymerizing an olefin in the presence of the component (a), the component (b), the carrier (c) and the component (d) optionally used. The prepolymerization can be carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of the component (a), the component (b), the carrier (c) and the component (d) optionally used.
Examples of the olefins used in the prepolymerization include ethylene and xcex1-olefins of 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-tetradecene. Of these, particularly preferable is ethylene or a combination of ethylene and the same xcex1-olefin as used in the polymerization.
In the prepolymerization, the component (a) is used in an amount of usually 10xe2x88x926 to 2xc3x9710xe2x88x922 mol/liter, preferably 5xc3x9710xe2x88x925 to 10xe2x88x922 mol/liter, and the component (a) is used in an amount of 5xc3x9710xe2x88x926 to 5xc3x9710xe2x88x924 mol, preferably 10xe2x88x925 to 2xc3x9710xe2x88x924 mol, based on 1 g of the carrier (c). The atomic ratio (Al/transition metal) of aluminum in the component (b) to the transition metal in the component (a) is in the range of usually 10 to 500, preferably 20 to 200. The atomic ratio (Al-d/Al-b) of an aluminum atom (Al-d) in the component (d) optionally used to an aluminum atom (Al-b) in the component (b) is in the range of usually 0.02 to 3, preferably 0.05 to 1.5. The prepolymerization temperature is in the range of usually xe2x88x9220 to 80xc2x0 C., preferably 0 to 60xc2x0 C., and the prepolymerization time is in the range of usually 0.5 to 100 hours, preferably about 1 to 50 hours.
The prepolymerized catalyst is prepared by, for example, the following process. The carrier (c) is suspended in an inert hydrocarbon to give a suspension. To the suspension, the organoaluminum oxy-compound (component (b)) is added, and they are reacted for a given period of time. Then, the supernatant liquid is removed, and the resulting solid is resuspended in an inert hydrocarbon. To the system, the transition metal compound (component (a)) is added, and they are reacted for a given period of time. Then, the supernatant liquid is removed to obtain a solid catalyst component. Subsequently, to an inert hydrocarbon containing the organoaluminum compound (component (d)), the solid catalyst component obtained above is added and an olefin is further introduced, whereby a prepolymerized catalyst is obtained.
In the prepolymerization, an olefin polymer is desirably produced in an amount of 0.1 to 500 g, preferably 0.2 to 300 g, more preferably 0.5 to 200 g, based on 1 g of the carrier (c). In the prepolymerized catalyst, the component (a) is desirably supported in an amount of about 5xc3x9710xe2x88x926 to 5xc3x9710xe2x88x924 gxc2x7atom, preferably 10xe2x88x925 to 2xc3x9710xe2x88x924 gxc2x7atom, in terms of the transition metal atom, based on 1 g of the carrier (c); and the aluminum atom derived from the component (b) and the component (d) is desirably supported in such an amount that the molar ratio (Al/M) of the aluminum atom (Al) to the transition metal atom (M) derived from the component (a) becomes 5 to 200, preferably 10 to 150.
The prepolymerization can be carried out by any of batchwise and continuous processes, and can be carried out under reduced pressure, at atmospheric pressure or under pressure. In the prepolymerization, it is desirable that hydrogen is allowed to be present in the system to produce a prepolymer having an intrinsic viscosity (xcex7), as measured in decalin at 135xc2x0 C., of 0.2 to 7 dl/g, preferably 0.5 to 5 dl/g.
The ethylene/xcex1-olefin copolymer (A) for use in the invention is obtained by copolymerizing ethylene and an xcex1-olefin of 6 to 20 carbon atoms in the presence of the olefin polymerization catalyst or the prepolymerized catalyst described above.
In the present invention, copolymerization of ethylene and an xcex1-olefin is carried out in a gas phase or a liquid phase of slurry. In the slurry polymerization, an inert hydrocarbon may be used as the solvent, or the olefin itself may be used as the solvent.
Examples of the inert hydrocarbon solvents used in the slurry polymerization include aliphatic hydrocarbons, such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons, such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane; aromatic hydrocarbons, such as benzene, toluene and xylene; and petroleum fractions, such as gasoline, kerosine and gas oil. Of the inert hydrocarbon media, preferable are aliphatic hydrocarbons, alicyclic hydrocarbons and petroleum fractions.
When the copolymerization is carried out as slurry polymerization or gas phase polymerization, the olefin polymerization catalyst or the prepolymerized catalyst is desirably used in an amount of usually 10xe2x88x928 to 10xe2x88x923 gxc2x7atom/liter, preferably 10xe2x88x927 to 10xe2x88x924 gxc2x7atom/liter, in terms of a concentration of the transition metal atom in the polymerization reaction system.
In the polymerization, an organoaluminum oxy-compound similar to the component (b) and/or the organoaluminum compound (d) may be added. In this case, the atomic ratio (Al/M) of an aluminum atom (Al) derived from the organoaluminum oxy-compound and the organoaluminum compound to the transition metal atom (M) derived from the transition metal compound (a) is in the range of 5 to 300, preferably 10 to 200, more preferably 15 to 150.
When the slurry polymerization is conducted, the polymerization temperature is in the range of usually xe2x88x9250 to 100xc2x0 C., preferably 0 to 90xc2x0 C. When the gas phase polymerization is conducted, the polymerization temperature is in the range of usually 0 to 120xc2x0 C., preferably 20 to 100xc2x0 C.
The polymerization pressure is in the range of usually atmospheric pressure to 100 kg/cm2, preferably 2 to 50 kg/cm2. The polymerization can be carried out by any of batchwise, semi-continuous and continuous processes, and can be carried out in not only plural stages but also plural stages such as two stages.
It is possible to conduct copolymerization in two or more stages under different conditions using one or plural polymerization reactors.
To the ethylene/xcex1-olefin copolymer (A) for use in the invention, various additives, such as weathering stabilizer, heat stabilizer, antistatic agent, anti-slip agent, anti-blocking agent, anti-fogging agent, lubricant, pigment, dye, nucleating agent, plasticizer, anti-aging agent, hydrochloric acid absorbent and antioxidant, may be optionally added in amounts not detrimental to the objects of the present invention. Further, other polymer compounds may be blended in small amounts without departing from the spirit of the invention.
The second ethylene resin packaging film according to the invention is made of an ethylene/xcex1-olefin copolymer composition (B). The ethylene/xcex1-olefin copolymer composition (B) is described below.
The ethylene/xcex1-olefin copolymer composition (B) for use in the invention comprises an ethylene/xcex1-olefin copolymer (a-1) and high-density polyethylene (b-1).
In the ethylene/xcex1-olefin copolymer composition (B), the ethylene/xcex1-olefin copolymer (a-1) is contained in an amount of 50 to 99 parts by weight, preferably 50 to 90 parts by weight, more preferably 55 to 80 parts by weight, and the high-density polyethylene (b-1) is contained in an amount of 1 to 50 parts by weight, preferably 10 to 50 parts by weight, more preferably 20 to 45 parts by weight.
Similarly to the ethylene/xcex1-olefin copolymer (A), the ethylene/xcex1-olefin copolymer (a-1) is preferably a copolymer obtained by copolymerizing ethylene and an xcex1-olefin of 6 to 20 carbon atoms in the presence of an olefin polymerization catalyst comprising (a) a compound of a transition metal of Group IV of the periodic table, said compound (a) containing a ligand having cyclopentadienyl skeleton, and (b) an organoaluminum oxy-compound.
The catalyst components are identical with the catalyst components previously described.
The ethylenelxcex1-olefin copolymer (a-1) desirably has the following properties:
(i) the density is in the range of 0.900 to 0.935 g/cm3,
(ii) the melt flow rate (MFR (g/10 min)) at 190xc2x0 C. under a load of 2.16 kg is in the range of 0.01 to 1.0 g/10 min,
(iii) the decane-soluble component fraction (W (% by weight)) at room temperature and the density (d (g/cm3)) satisfy the following relation
W less than 80xc3x97exp(xe2x88x92100(dxe2x88x920.88))+0.1,
(iv) the flow index (FI (l/sec)), which is defined as a shear rate at which the shear stress of said copolymer in a molten state at 190xc2x0 C. reaches 2.4xc3x97106 dyne/cm2, and the melt flow rate (MFR (g/10 min)) satisfy the following relation
FI greater than 75xc3x97MFR,
(v) the melt tension (MT (g)) at 190xc2x0 C. and the melt flow rate (MFR (g/10 min)) satisfy the following relation
MT greater than 2.2xc3x97MFRxe2x88x920.84,
preferably 5.5xc3x97MFRxe2x88x920.65 greater than MT greater than 2.2xc3x97MFRxe2x88x920.84, and
the temperature (Tm (xc2x0 C.)) at the maximum peak position in an endothermic curve of said copolymer (a-1), as measured by a differential scanning calorimeter (DSC), and the density (d) satisfy the following relation
Tm less than 400dxe2x88x92250.
Next, the high-density polyethylene (b-1) is described.
The high-density polyethylene (b-1) is a homopolymer of ethylene or a copolymer of ethylene and an xcex1-olefin of 3 to 20 carbon atoms.
The high-density polyethylene (b-1) desirably has a density of 0.935 to 0.975 g/cm3, preferably 0.935 to 0.965 g/cm3.
The high-density polyethylene (b-1) desirably has a melt flow rate (MFR (g/10 min)), as measured at 190xc2x0 C. under a load of 2.16 kg, of 0.1 to 100 g/10 min, preferably 0.5 to 80 g/10 min.
For preparing the high-density polyethylene (b-1), any of known polymerization processes is employable, as far as the resulting polyethylene has the above properties. The high-density polyethylene (b-1) is preferably one prepared by the use of a titanium catalyst component or a metallocene catalyst component.
The ethylene/xcex1-olefin copolymer composition (B) for use in the invention can be prepared by known processes, for example, the following processes.
(1) The ethylene/xcex1-olefin copolymer (a-1), the copolymer (b-1) and other components optionally used are mechanically blended using an extruder, a kneader or the like.
(2) The ethylene/xcex1-olefin copolymer (a-1), the copolymer (b-1) and other components optionally used are dissolved in an appropriate good solvent (e.g., hydrocarbon solvent, such as hexane, heptane, decane, cyclohexane, benzene, toluene or xylene), and the solvent is then removed.
(3) The ethylene/xcex1-olefin copolymer (a-1), the copolymer (b-1) and other components optionally used are each dissolved in an appropriate good solvent to prepare solutions, then the solutions are mixed, and the solvents are removed.
(4) The processes (1) to (3) are carried out in combination.
Other than the above-mentioned processes, the following processes can be used to prepare the ethylene/xcex1-olefin copolymer composition (B).
Using one polymerization reactor, the polymerization is conducted in two or more stages under different conditions to prepare the ethylene/xcex1-olefin copolymer (a-1) and the copolymer (b-1). More specifically, in a two-stage polymerization process, the ethylene/xcex1-olefin copolymer (a-1) is produced in the former stage and the copolymer (b-1) is produced in the latter stage, or the copolymer (b-1) is produced in the former stage and the ethylene/xcex1-olefin copolymer (a-1) is produced in the latter stage, whereby the composition (B) can be prepared.
Otherwise, using plural polymerization reactors, the ethylene/xcex1-olefin copolymer (a-1) is produced in one reactor and the copolymer (b-1) is then produced in another reactor in the presence of the ethylene/xcex1-olefin copolymer (a-1), or the copolymer (b-1) is produced in one reactor and the ethylene/xcex1-olefin copolymer (a-1) is then produced in another reactor in the presence of the copolymer (b-1), whereby the composition (B) can be prepared.
The ethylene/xcex1-olefin copolymer composition (B) can be favorably used for packaging films.
To the ethylene/xcex1-olefin copolymer composition (B) for use in the invention, various additives, such as weathering stabilizer, heat stabilizer, antistatic agent, anti-slip agent, anti-blocking agent, anti-fogging agent, lubricant, pigment, dye, nucleating agent, plasticizer, anti-aging agent, hydrochloric acid absorbent and antioxidant, may be optionally added in amounts not detrimental to the objects of the present invention. Further, other polymer compounds may be blended in small amounts without departing from the spirit of the invention.
The third ethylene resin packaging film according to the invention is made of an ethylene/xcex1-olefin copolymer composition (C). The ethylene/xcex1-olefin copolymer composition (C) is described below.
The ethylene/xcex1-olefin copolymer composition (C) for use in the invention comprises an ethylene/xcex1-olefin copolymer (a-2) and an ethylene copolymer (b-2).
In the ethylene/xcex1-olefin copolymer composition (C), the ethylene/xcex1-olefin copolymer (a-2) is contained in an amount of 1 to 50 parts by weight, preferably 3 to 40 parts by weight, more preferably 5 to 35 parts by weight, and the ethylene copolymer (b-2) is contained in an amount of 50 to 99 parts by weight, preferably 60 to 97 parts by weight, more preferably 65 to 95 parts by weight.
The ethylene/xcex1-olefin copolymer (a-2) is preferably a copolymer obtained by copolymerizing ethylene and an xcex1-olefin of 4 to 12 carbon atoms in the presence of an olefin polymerization catalyst comprising (a) a compound of a transition metal of Group IV of the periodic table, said compound (a) containing a ligand having cyclopentadienyl skeleton, and (b) an organoaluminum oxy-compound.
The catalyst components are identical with the catalyst components previously described.
The ethylene/xcex1-olefin copolymer (a-2) desirably has the following properties:
(i) the density is in the range of 0.880 to 0.925 g/cm3,
(ii) the melt flow rate (MFR (g/10 min)) at 190xc2x0 C. under a load of 2.16 kg is in the range of 0.01 to 5.0 g/10 min,
(iii) the decane-soluble component fraction (W (% by weight)) at room temperature and the density (d (g/cm3)) satisfy the following relation
W less than 80xc3x97exp(xe2x88x92100(dxe2x88x920.88))+0.1,
(iv) the flow index (FI (l/sec)), which is defined as a shear rate at which the shear stress of said copolymer in a molten state at 190xc2x0 C. reaches 2.4xc3x97106 dyne/cm2, and the melt flow rate (MFR (g/10 min)) satisfy the following relation
FI greater than 75xc3x97MFR, and
(v) the melt tension (MT (g)) at 190xc2x0 C. and the melt flow rate (MFR (g/10 min)) satisfy the following relation MT greater than 2.2xc3x97MFRxe2x88x920.84,
preferably 5.5xc3x97MFRxe2x88x920.65 greater than MT greater than 2.2xc3x97MFRxe2x88x920.84.
Next, the ethylene copolymer (b-2) is described.
The ethylene copolymer (b-2) is a copolymer obtained by copolymerizing ethylene and an xcex1-olefin of 4 to 10 carbon atoms.
The ethylene copolymer (b-2) desirably has a density of 0.920 to 0.945 g/cm3, preferably 0.920 to 0.935 g/cm3.
The ethylene copolymer (b-2) desirably has a melt flow rate (MFR (g/10 min)), as measured at 190xc2x0 C. under a load of 2.16 kg, of 0.1 to 10 g/10 min, preferably 0.1 to 8 g/10 min.
The ethylene copolymer (b-2) desirably has a ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), Mw/Mn, ranging from 3 to 6.
For preparing the high-density polyethylene (b-2), any of known polymerization processes is employable, as far as the resulting copolymer has the above properties. The ethylene copolymer (b-2) is preferably one prepared by the use of a titanium catalyst component.
The ethylene/xcex1-olefin copolymer composition (C) for use in the invention can be prepared by known processes, for example, the aforesaid processes.
The ethylene/xcex1-olefin copolymer composition (C) can be favorably used for packaging films.
The first ethylene resin packaging film according to the invention can be produced by feeding the ethylene/xcex1-olefin copolymer (A) to an inflation film molding machine or an extrusion molding machine equipped with a T-die.
The second ethylene resin packaging film according to the invention can be produced by feeding the ethylene/xcex1-olefin copolymer composition (B) to an inflation film molding machine or an extrusion molding machine equipped with a T-die. In the production of the film of the ethylene/xcex1-olefin copolymer composition (B), the components in the form of pellets may be mixed and then directly fed to the extrusion molding machine, or the components may be mixed by means of a commonly used mixing machine such as a Henschel mixer, a tumbling mixer, a single-screw extruder or a twin-screw extruder and then fed to the extrusion molding machine for film production.
The first and the second ethylene resin packaging films have a Young""s modulus, as measured in accordance with JIS K 6781, of not less than 4,000 kg/cm2, preferably 4,000 to 10,000 kg/cm2, a dart impact strength, as measured in accordance with the method A of ASTM D 1709, of not less than 55 kg/cm, preferably 55 to 150 kg/cm, and a film thickness of usually 30 to 200 xcexcm.
The first and the second ethylene resin packaging films can be satisfactorily used for heavy-duty packaging bags even in the cold districts having below-zero temperatures. These ethylene resin packaging films have excellent low-temperature properties, so that the film thickness can be made smaller and high-speed film molding is feasible.
The third ethylene resin packaging film according to the invention is a film produced by air-cooling inflation of the ethylene/xcex1-olefin copolymer composition (C).
The third ethylene resin packaging film has Young""s modulus, as measured in accordance with JIS K 6781, of not less than 250 kg/cm2, preferably 250 to 1,000 kg/cm2, an Elmendorf tear strength in the machine direction, as measured by a tear test in accordance with ASTM D-1922, of not less than 55 kg/cm, preferably 55 to 150 kg/cm, and a film thickness of usually about 10 to 100 xcexcm.
The third ethylene resin packaging film exhibits excellent mechanical strength properties such as high dart impact strength and Elmendorf tear strength with retaining properties inherent in films of linear low-density polyethylene, such as transparency and surface smoothness. In addition, high-speed film molding is feasible.
The packaging films of the present invention retain properties inherent in films of linear low-density polyethylene, such as transparency and surface smoothness.
Moreover, the films of the invention exhibit excellent mechanical strength properties such as high dart impact strength with retaining properties inherent in films of linear low-density polyethylene, such as transparency and surface smoothness. Further, high-speed film molding is feasible. Therefore, thin films having such excellent properties can be produced with high productivity.
From the resin composition for the films of the invention, which exerts the above effects, single-layer films can be produced, and besides multi-layer films can be also produced by laminating the composition with other films such as films of polyester and polyamide. These films are suitable for packaging foods, office supplies, furniture, toys, electrical equipment, machine parts and the like.
The ethylene resin packaging films of the invention can be satisfactorily used for heavy-duty packaging bags even in the cold districts having below-zero temperatures.